WO2019030250A1 - Compositions de polyamide ignifuges et leur utilisation - Google Patents

Compositions de polyamide ignifuges et leur utilisation Download PDF

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Publication number
WO2019030250A1
WO2019030250A1 PCT/EP2018/071443 EP2018071443W WO2019030250A1 WO 2019030250 A1 WO2019030250 A1 WO 2019030250A1 EP 2018071443 W EP2018071443 W EP 2018071443W WO 2019030250 A1 WO2019030250 A1 WO 2019030250A1
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component
flame
proportion
polyamide compositions
compositions according
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PCT/EP2018/071443
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German (de)
English (en)
Inventor
Harald Bauer
Sebastian HÖROLD
Martin Sicken
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Clariant Plastics & Coatings Ltd
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Priority to EP18752739.5A priority Critical patent/EP3665218A1/fr
Priority to JP2020506708A priority patent/JP7252199B2/ja
Priority to KR1020207007106A priority patent/KR102601778B1/ko
Priority to US16/637,833 priority patent/US20200172709A1/en
Publication of WO2019030250A1 publication Critical patent/WO2019030250A1/fr

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
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    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
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    • C08L2203/20—Applications use in electrical or conductive gadgets
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to flame-retardant polyamide compositions and molded articles made therefrom.
  • Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislation. Preference - also for ecological reasons - are non-halogenated
  • dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, the polymer only undergoing very little degradation upon incorporation of the flame retardant into the polymer matrix.
  • Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the
  • Flame retardant especially at higher dosages, the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration.
  • Polyamide compositions that achieve all the required properties at the same time, such as a good flowability, good electrical properties and effective flame retardancy, at the same time no discoloration tendencies occur.
  • Polyamide having a melting point of less than or equal to 290 ° C, preferably of less than or equal to 280 ° C and most preferably of less than or equal to 250 ° C, as component A,
  • Ri and R2 are ethyl
  • M is Al, Fe, TiOp or Zn
  • n 2 to 3, preferably 2 or 3
  • R 3 is ethyl
  • Met is Al, Fe, TiOq or Zn
  • n 2 to 3, preferably 2 or 3
  • Melaminpolyphosphat having an average degree of condensation of 2 to 200 as component F, sterically hindered phenolic antioxidant component G, and / or organic phosphite and / or organic phosphonite as component H.
  • the proportion of component A is usually 25 to 95 wt .-%, preferably 25 to 75 wt .-%.
  • the proportion of component B is usually 1 to 45% by weight, preferably 20 to 40% by weight.
  • the proportion of component C is usually 1 to 35 wt .-%, preferably 5 to 20 wt .-%.
  • the proportion of component D is usually 0.01 to 3 wt .-%, preferably 0.05 to
  • the proportion of component E is usually 0.001 to 1 wt .-%, preferably 0.01 to
  • the proportion of component F is usually 1 to 25 wt .-%, preferably 2 to 10 wt .-%.
  • the content of the component G is usually 0.01 to 5% by weight, preferably 0.5 to 1% by weight.
  • the proportion of component H is usually 0.01 to 5 wt .-%, preferably 0.5 to 1 wt .-%.
  • the percentages for the proportions of components A to H refer to the total amount of the polyamide composition.
  • the proportion of component B is from 1 to 45% by weight
  • the proportion of component E is 0.001 to 1% by weight, the proportion of component F 1 to 25% by weight,
  • the proportion of component H is 0.05 to 5% by weight
  • the proportion of component A is from 25 to 75% by weight
  • the proportion of component B is from 20 to 40% by weight
  • the proportion of component C is from 5 to 20% by weight
  • the proportion of component D is 0.05 to 1.5% by weight
  • the proportion of component E is from 0.01 to 0.6% by weight
  • Preferred salts of component C are those in which M m + Zn 2+ , Fe 3 ' or in particular Al 3+ .
  • Preferably used salts of component D are zinc, iron or
  • Preferably used salts of component E are those in which Met n + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • the above-described flame retardant polyamide compositions contain inorganic phosphonate as further component I.
  • the inorganic phosphonate (component I) preferably corresponds to the general formulas (IV) or (V)
  • Kat is a p-valent cation, in particular a cation of an alkali metal, alkaline earth metal, an ammonium cation and / or a cation of Fe, Zn or particular AI including the cation AI ( OH) or Al (OH) 2, and p is 1, 2, 3 or 4.
  • the inorganic phosphonate (component I) is preferably also aluminum phosphites of the formulas (VI), (VII) and / or (VIII)
  • M is alkali metal cations, z is 0.01 to 1.5, and y is 2.63 to 3.5 and v is 0 to 2 and w is 0 to 4; Al 2, oo (HPO 3) u (H 2 PO 3) t x (H 2 O) s (VIII), where u is 2 to 2.99 and 1 2 to 0.01 and s is 0 to 4, and / or
  • Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 * 4aq] to give aluminum phosphonate to Al7 (HPO 3) 9 (OH) 6 (1,6-hexanediamine) i, 5 * 12H 2 O, by ⁇ 2 ( ⁇ 3 ) 3 * ⁇ 2 ⁇ 3 * ⁇ 2 ⁇ with x 2.27 - 1 and / or AUHePieOis.
  • Preferred inorganic phosphonates (component I) are water-insoluble or sparingly soluble salts.
  • Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.
  • component F is a
  • Reaction product of phosphorous acid and an aluminum compound Reaction product of phosphorous acid and an aluminum compound.
  • Particularly preferred components F are aluminum phosphites with the
  • the preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days.
  • the aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried.
  • Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
  • Preferred sources of phosphorus are phosphorous acid, (acidic)
  • Preferred alkali metal phosphites are disodium phosphite, Dinat umphosphithydrat, trisodium phosphite, potassium hydrogen phosphite
  • Preferred disodium phosphite hydrate is ⁇ Brüggolen H10 from Brüggemann.
  • Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
  • Preferred alkaline earth metal phosphite is calcium phosphite.
  • the preferred ratio of aluminum to phosphorus to solvent is 1: 1: 3.7 to 1: 2.2: 100 mol.
  • the ratio of aluminum to template is 1: 0 to 1: 17 mol.
  • the preferred pH of the reaction solution is 3 to 9.
  • Preferred solvent is water.
  • the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
  • phosphinic acid aluminum diethylphosphinate together with aluminum phosphite or Zinkdiethylphosphinat together with zinc phosphite.
  • the above-described flame retardant polyester compositions contain as component I
  • Me is Fe, TiOr, Zn or in particular Al,
  • o is 2 to 3, preferably 2 or 3
  • Preferred compounds of the formula III are those in which Me is O + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • Component I is preferably in an amount of 0.005 to 10 wt .-%, in particular in an amount of 0.02 to 5 wt .-%, based on the
  • Polyamide compositions having a Comparative Tracking Index measured according to the International Electrotechnical Commission Standard IEC-601 12/3, of greater than 500 volts.
  • Polyamide compositions achieve a rating of V0 according to UL-94, in particular measured on moldings of 3.2 mm to 0.4 mm thickness. Further preferred flame-retardant according to the invention
  • Polyamide compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C, in particular measured
  • the polyamide compositions of the invention contain as component A one or more polyamides having a melting point of less than or equal to 290 ° C. The melting point is determined by means of differential scanning caloimetry (DSC) at a heating rate of 10 K / second.
  • the polyamides of component A are generally homo- or copolyamides derived from (cyclo) aliphatic dicarboxylic acids or their polyamide-forming derivatives, such as their salts, and from (cyclo) aliphatic Diamines or derived from (cyclo) aliphatic aminocarboxylic acids or their polyamide-forming derivatives, such as their salts.
  • the polyamides used as component A according to the invention are thermoplastic polyamides.
  • thermoplastic polyamides are based on Hans
  • polyamides according to the invention used as component A can be prepared by various methods and synthesized from very different building blocks and in a specific application alone or in combination with processing aids, stabilizers or polymers
  • Alloy partners preferably elastomers, to materials equipped with specially selected property combinations. are also suitable
  • Monomerbausteine various chain regulators for setting a desired molecular weight or monomers with reactive groups for later intended post-treatments can be used.
  • the technically relevant processes for the preparation of polyamides usually run via the polycondensation in the melt.
  • the hydrolytic polymerization of lactams is understood as a polycondensation.
  • Polyamides to be preferably used as component A are partially crystalline aliphatic polyamides starting from aliphatic diamines and
  • aliphatic dicarboxylic acids and / or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids can be prepared.
  • Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane,
  • Aminocarboxylic acids preferably aminocaproic acid or the corresponding lactams into consideration.
  • Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ⁇ -caprolactam is used.
  • the aliphatic homo- or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6,
  • Polyamide 6 polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12,
  • PA6 PA6.6
  • other aliphatic homo- or copolyamide-based compounds in which a
  • Polyamide group in the polymer chain 3 to 1 1 come methylene groups.
  • Flame-dense polyamide compositions in which one or more polyamides are selected as component A from the group consisting of PA 6, PA 6.6, PA 4.6, PA 12, PA 6.10 are preferably used.
  • Flame-retardant polyamide compositions in which polyamide 6.6 or polymer mixtures are used as component A are particularly preferred
  • Polyamide 6.6 and polyamide 6 are used.
  • component B fillers and / or preferably reinforcing materials are used, preferably glass fibers. It is also possible to use mixtures of two or more different fillers and / or reinforcing materials.
  • Preferred fillers are mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmites, magnesium carbonate, chalk, feldspar, glass beads and / or barium sulfate. Particular preference is given to mineral particulate fillers based on talc, wollastonite and / or kaolin.
  • needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character. Preferred are needle-shaped wollastonites.
  • the mineral has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1.
  • the average particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 ⁇ m. more preferably at less than 15 ⁇ , more preferably at less than 10 ⁇ , determined with a CILAS granulometer.
  • the components B preferably used according to the invention are reinforcing materials. This may, for example, to
  • Reinforcement based on carbon fibers and / or glass fibers act.
  • the filler and / or reinforcing material may in a preferred
  • Be surface-modified embodiment preferably with a
  • Adhesive or a primer system particularly preferably on
  • Silane In particular when glass fibers are used, in addition to silanes, polymer dispersions, film formers, branching agents and / or
  • Fiber processing aids are used.
  • the glass fibers preferably used according to the invention as component B may be short glass fibers and / or long glass fibers. As short or long glass fibers, cut fibers can be used. Short glass fibers can also be used in the form of ground glass fibers.
  • glass fibers can also be used in the form of continuous fibers, for example in the form of rovings, monofilaments,
  • Filament yarns or twines or glass fibers can be used in the form of textile fabrics, for example as glass fabrics, as
  • Glass braid or as a glass mat Glass braid or as a glass mat.
  • Polyamide matrix range from 0.05 to 10 mm, preferably from 0.1 to 5 mm. After incorporation into the polyamide matrix, the length of the glass fibers has decreased. Typical fiber lengths for short glass fibers after the
  • Incorporation into the polyamide matrix ranges from 0.01 to 2 mm, preferably from 0.02 to 1 mm.
  • the diameters of the individual fibers can vary within wide ranges. Typical diameters of the individual fibers range from 5 to 20 ⁇ m.
  • the glass fibers can have any cross-sectional shapes, for example round, elliptical, n-cornered or irregular cross-sections. Glass fibers with mono- or multilobal cross-sections can be used.
  • Glass fibers can be used as continuous fibers or as cut or ground glass fibers.
  • the glass fibers themselves can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,
  • the glass fibers are preferably provided with a size which preferably contains polyurethane as film former and aminosilane as adhesion promoter.
  • Particularly preferably used E glass fibers have the following chemical
  • R glass fibers have the following chemical composition: S1O2 50-65%; AI2O3 20-30%; CaO 6-16%; MgO 5-20%; Na 2 O 0.3-0.5%; K2O 0.05-0.2%; Fe 2 Os 0.2-0.4%, ⁇ 2 0.1 -0.3%.
  • ECR glass fibers have the following chemical composition: S1O2 57.5-58.5%; AI2O3 17.5-19.0%; CaO 11, 5-13.0%; MgO 9.5-1 1, 5.
  • the salts of diethylphosphinic acid used according to the invention as component C are known flame retardants for polymers
  • Component C may contain small amounts of salts of component D and salts of component E, for example up to 10 wt .-% of
  • Component D preferably 0.01 to 6% by weight, and in particular 0.2 to 2.5% by weight thereof, and up to 10% by weight of component E, preferably 0.01 to 6% by weight, and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components C, D and E.
  • Ethylphosphonic acid are as additives to Diethylphosphinaten in
  • Flame retardants for polymeric molding compositions also known, for example from WO 2016/065971 A1.
  • DE 10 2005 016 195 A1 discloses a stabilized flame retardant containing 99 to 1% by weight.
  • Phosphinic acid and / or a phosphinic acid salt can be combined.
  • Preferred flame retardant polyamide compositions according to the invention contain, as component F, a melamine polyphosphate whose average degree of condensation is from 20 to 200, in particular from 40 to 150. In another preferred range, the average degree of condensation is 2 to 100. Further preferred flame-retardant according to the invention
  • Polyamide compositions contain as component F a
  • Melaminpolyphosphat having a decomposition temperature greater than or equal to 320 ° C, in particular greater than or equal to 360 ° C and most preferably greater than or equal to 400 ° C.
  • melamine polyphosphates which are known from WO 2006/027340 A1 (corresponding to EP 1 789 475 B1) and WO 2000/002869 A1 (corresponding to EP 1 095 030 B1). Preference is given to using melamine polyphosphates whose average degree of condensation is between 20 and 200, in particular between 40 and 150, and whose melamine content is 1.1 to 2.0 mol, in particular 1.2 to 1.8 mol, per mole of phosphorus atom.
  • melamine polyphosphates whose mean condensation ridge (number average) is> 20 whose decomposition temperature is greater than 320 ° C., the molar ratio of 1,3,5-triazine compound to phosphorus being less than 1, 1, in particular 0.8 to 1, Is 0 and the pH of a 10% slurry in water at 25 ° C is 5 or higher, preferably 5.1 to 6.9.
  • components C, D, E and F are in particulate form, the average particle size (dso) being 1 to 100 ⁇ m.
  • the sterically hindered phenols added as component G according to the invention are known antioxidants.
  • Antioxidants preferably used as component G are alkylated
  • Monophenols e.g. As 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4- methoxyphenol; sterically hindered alkylthiomethylphenols, e.g. B. 2,4-di-octylthiomethyl-6-tert-butylphenol, sterically hindered hydroxylated
  • Thiodiphenyl ether e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 4,4'-thio-bis (6-tert-butyl-3-methyl-phenol), 4,4'- Thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6- di-methyl-4-hydroxyphenyl) disulfide; sterically hindered alkylidene bisphenols, e.g. B.
  • 2,2'-methylenebis (6-tert-butyl-4-methylphenol; sterically hindered benzylphenols, eg 3,5,3 ', 5'-tetra-tert-butyl-4,4' hindered hydroxybenzylated malonates, eg, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate; hindered hydroxybenzyl aromatics, eg, 1 , 3,5-Tris (3,5-di-tert-butyl) -4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3,5-di-tert-butyl 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol; sterically hindered phenolic triazine compounds, e
  • Benzylphosphonates e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate; N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbaminklarealkylester; Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols; Esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols; Amides of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) -propi
  • Phosphites and / or organic phosphonites are known co-stabilizers for antioxidants.
  • Organic phosphites have the general formula P (OR) 3, wherein R are monovalent organic radicals.
  • Organic phosphonites have the general formula PFT (OR) 2, where R and R 'are monovalent organic radicals.
  • organic phosphites examples include triaryl phosphites,
  • triaryl phosphites are triphenyl phosphites, in particular tris (nonylphenyl) phosphite or tris (2,4-di-tert-butylphenyl) phosphite.
  • diarylalkyl phosphites are diphenylalkyl phosphites, in particular bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite or bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
  • Aryldialkylphosphite examples include Phenyldialkylphosphite.
  • trialkyl phosphites are C 12-C 18 trialkyl phosphites, in particular trilauryl phosphite or trioctadecyl phosphite.
  • Examples of further suitable organic phosphites are pentaerythritol diphosphites, such as distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite or bis (2,4,6-tris (tert-butylphenyl)) pentaerythritol diphosphite.
  • pentaerythritol diphosphites such as distearyl pent
  • organophosphites are tristearyl sorbitol triphosphite, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl ) phosphite] or
  • R 4 is a mono- or polyhydric aliphatic, aromatic or heteroaromatic organic radical and Rs is a structure of the formula (V)
  • A is a direct bond, O, S, linear or branched C-18-alkylene, linear or branched C-18-alkylidene,
  • R 6 independently of one another are linear or branched C 1-12 -alkyl, linear or branched C 1-12 -alkoxy and / or C 5-12 -cycloalkyl,
  • p 1 to 4.
  • C4-18-alkylene C5-i2-cycloalkyl, C5-i2-cycloalkylene, C6-24-aryl or -heteroaryl, C6-24 arylene or heteroarylene, which may be further
  • Rs are radicals of the formula (V) or (VI)
  • R 1 independently of one another are linear or branched C 1-8 -alkyl, linear or branched C 1-8 -alkoxy or cyclohexyl
  • A is a direct bond
  • O is linear or branched Ci-8-alkylene, linear or branched Ci-8-alkylidene
  • q is 0 to 3
  • p is 1 to 3.
  • Phosphonites of the formula IV are particularly preferably used as component H, wherein radical R 4 is cyclohexyl, phenyl, phenylene, biphenyl or biphenylene, R 5 are radicals of the formulas V or VI, where Re independently of one another is linear or branched C 1-8 -alkyl, linear or branched Ci-8-alkoxy or cyclohexyl, A is a direct bond, O or linear or branched Ci-6-alkylidene, q is 1 to 3, and p is 1 or 2.
  • Particularly preferred components H are compounds which, based on the above definitions, are obtained by a Friedel-Crafts reaction of an aromatic or heteroaromatic, such as benzene, biphenyl or diphenyl ether with phosphorus trifluoride, preferably phosphorus trichloride, in the presence of a Friedel-Crafts catalyst, such as aluminum chloride, zinc chloride or ferric chloride as well
  • n can be 0 or 1 and these mixtures can optionally also still contain fractions of the following compounds:
  • Very particularly preferred components H are 1, 1 -biphenyl-4,4 '- diylbisphosphonite and tetrakis thereof especially (2,4-di-tert-butylphenyl) - [1, 1 - biphenyl] -4,4'-diylbisphosphonit ( P-EPQ).
  • component GN N'-bis - ⁇ - di-tert-butyl ⁇ - hydroxyphenyl) propionyl] hexamethylenediamine (eg Irganox ® 1098, BASF) and as component H tris (2,4-di-tert butylphenyl) phosphite (z. B. Irgaphos 168 ®, BASF) was used.
  • component GN N'-bis - ⁇ - di-tert-butyl ⁇ - hydroxyphenyl) propionyl] hexamethylenediamine (eg Irganox ® 1098, BASF) and as component H tetrakis (2,4-di -tert-butylphenyl) -.
  • [1, 1-biphenyl] -4,4'-diylbisphosphonit eg Sandostab ® P-EPQ, Clariant was used.
  • the polyamide compositions according to the invention may contain further additives as component J.
  • Preferred components J for the purposes of the present invention are further antioxidants which are not steric hindered phenols, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants which are not organic phosphites, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and / or other flame retardants derived from C components , D, E, F and I differ.
  • phosphates such as melamine poly (metal phosphates).
  • metal phosphates such as melamine poly (metal phosphates).
  • Preferred metals for this purpose are the elements of FIG. 2.
  • Main group the 3rd main group, the 2nd subgroup, the 4th subgroup and the subgroup Villa of the Periodic Table and cerium and / or lanthanum.
  • Melamine poly (metal phosphates) are preferably melamine poly (zinc phosphates), melamine poly (magnesium phosphates) and / or melamine poly (calcium phosphates).
  • melamine poly (metal phosphates) which are known as
  • melamine-intercalated aluminum, zinc or magnesium salts of condensed phosphates very particular preference is given to bis-melamine-zinc-diphosphate and / or bis-melamine-alumotriphosphate.
  • Polyphosphates Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
  • calcium phosphate zinc phosphate, titanium phosphate and / or iron phosphate
  • Calcium dihydrogen pyrophosphate, magnesium pyrophosphate zinc pyrophosphate and / or aluminum pyrophosphate are examples of magnesium pyrophosphate and / or aluminum pyrophosphate.
  • DE-A-102007036465 and EP-A-31331 12 are expressly among the usable components I.
  • the other additives are known per se as additives to polyamide compositions and can be used alone or in admixture or in the form of masterbatches.
  • the abovementioned components A, B, C, D, E, F, G, H and, where appropriate, I and / or J can be used in a wide variety of combinations for
  • flame retarded polyamide composition according to the invention are processed. So it is possible, already at the beginning or at the end of the polycondensation or in a subsequent compounding process the components in the
  • two or more of the components of the polyamide compositions of the present invention may be combined by mixing prior to incorporation into the polyamide matrix.
  • conventional mixing units can be used, in which the components in a suitable mixer, for. B. 0.01 to 10 hours at 0 to 300 ° C mixed.
  • Polyamide compositions can also be prepared granules, which can then be introduced into the polyamide matrix.
  • Polyamide composition with granulation and / or binder in a suitable mixer or a granulating are processed into granules.
  • the initially formed crude product can be dried in a suitable dryer or tempered for further grain buildup.
  • the polyamide composition of the present invention or two or more components thereof may be prepared by roll compaction in one embodiment.
  • the polyamide composition according to the invention or two or more components thereof may in one embodiment be prepared by mixing, extruding, chopping (or breaking) the ingredients.
  • the polyamide composition of the present invention or two or more components thereof may be prepared by spray granulation in one embodiment.
  • the flame-retardant polymer molding composition according to the invention is preferably in granular form, for. B. as an extrudate or as a compound before.
  • the granules preferably have a cylindrical shape with a circular, elliptical or irregular base, spherical shape, pillow shape, cube shape, cuboid shape, prism shape.
  • Typical length to diameter ratio of the granules are 1 to 50 to 50 to 1, preferably 1 to 5 to 5 to 1.
  • the granules preferably have a diameter of 0.5 to 15 mm, more preferably of 2 to 3 mm and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm.
  • the invention also relates to moldings produced from the above-described flame-retardant polyamide composition comprising the components A, b, C, D, E, F, G and H and optionally the components I and / or J.
  • the molded parts according to the invention may be any desired formations.
  • Examples thereof are fibers, films or moldings obtainable from the flame-retardant polyamide molding compositions according to the invention by any desired molding processes, in particular by injection molding or extrusion.
  • the preparation of the flame-retardant polyamide molded body according to the invention can be carried out by any desired molding process. Examples are injection molding, pressing, foam injection molding, internal gas pressure injection molding, blow molding,
  • the molded parts are preferably injection-molded parts or extruded parts.
  • the flame-retardant polyamide compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.
  • the invention preferably relates to the use of the flame-retardant polyamide compositions according to the invention in or for connectors, current-carrying parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings,
  • Capacitor housings bobbins and fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible printed circuit boards, charging cables for mobile phones, engine covers or textile coatings.
  • the invention likewise preferably relates to the use of the flame-retardant polyamide compositions according to the invention for the production of
  • the wall thickness of the shaped bodies according to the invention can typically be up to 10 mm. Particularly suitable are moldings with less than 1, 5 mm Wall thickness, more preferably less than 1 mm wall thickness and more preferably less than 0.5 mm wall thickness.
  • Polyamide 6.6 (PA 6.6-GV; melting range of 255-260 ° C): Ultramid ® A27 (BASF)
  • Polyamide 6 (melting range of 217-222 ° C): Durethan ® B29 (Lanxess) polyamide 6T / 6,6 (melting range 310-320 ° C): Vestamid ® HAT plus 1000 (Evonik) glass fibers (component B):
  • Co-stabilizer H 1 (component H):
  • the flame retardant components were mixed in the proportions shown in the tables with the antioxidant and with the co-stabilizer and over the side feeder of a twin-screw extruder (Leistritz ZSE type
  • Injection molding machine type Arburg 320 C Allrounder
  • mass temperatures 250 to 320 ° C to test specimens processed and based on the UL 94 test
  • the flowability of the molding compositions was determined by determining the
  • MVR Melt volume index
  • the Comparative Tracking Index of the molded parts was determined according to the International Electrotechnical Commission Standard IEC-601 12/3.
  • the Glow Wire Flammability Index (GWFI Index) was standardized
  • polyamide compositions according to the invention of Examples 1 to 6, 1 a, 1 b and 5a are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, while having CTI 600 volts and GWFI 960 ° C, and none
  • Comparative Example V4 The omission of component F in Comparative Example V4 resulted in an increased MVR value and a reduced GWFI value in addition to a deterioration of the fire protection class compared to Example 2.
  • Comparative Example C5 was by increasing the concentration of
  • the polyamide compositions of Examples 7 to 12 according to the invention are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, at the same time CTI 600 volts and GWFI 960 ° C, and show no discoloration.
  • the addition of component I in Example 1 1 leads to a further improvement of the flame retardancy expressed by a reduced
  • Comparative Example V12 The omission of component F in Comparative Example V12 resulted in an increased MVR value and a reduced GWFI value in addition to a deterioration of the fire protection class compared to Example 8.
  • Comparative Example C13 was by increasing the concentration of
  • Polyamide composition still a lower compared to Example 8 fire protection class and an increased MVR value and a reduced GWFI value.
  • the polyamide compositions according to the invention of Examples 13 to 18 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm, at the same time have CTI 600 volts and GWFI 960 ° C., and show no discoloration.
  • the addition of component I in Example 17 leads to a further improvement of the flame retardancy expressed by a reduced
  • Comparative Example V20 The omission of component F in Comparative Example V20 resulted in an increased MVR value and a reduced GWFI value in addition to a deterioration of the fire protection class compared to Example 14.
  • Comparative Example V21 was by increasing the concentration of
  • Polyamide composition still a lower compared to Example 14 fire protection class and an increased MVR value and a reduced GWFI value.
  • G antioxidant 0.1 0, 0.1 0.1 0.1 0.1 0.1 H 1: Co-stabilizer 0, 1 0.1 0.1 0.1 0, 1 0.1 0.1
  • Test specimens could not be produced from any of the PA molding compositions of Comparative Examples V25-V32, since the PA molding compositions proved to be unprocessable.
  • the polyamide strands foamed during production and no test specimens suitable for the measurements could be produced.

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Abstract

L'invention concerne des compositions de polyamide ignifuges contenant du polyamide ayant un point de fusion inférieur ou égal à 290 °C en tant que constituant A, des substances de charge et/ou des substances de renfort en tant que constituant B; un sel d'acide phosphinique de formule (I) en tant que constituant C, où R1 et R2 sont éthyle, M est Al, Fe, TiOp ou Zn, m vaut de 2 à 3 et p = (4 - m) / 2; un composé choisi dans le groupe des sels d'Al, de Fe, de TiOp ou de Zn de l'acide éthylbutylphosphinique, de l'acide dibutylphosphinique, de l'acide éthylhexylphosphinique, de l'acide butylhexylphosphinique et/ou de l'acide dihexylphosphinique en tant que constituant D; un sel d'acide phosphonique de formule (II) en tant que constituant E, où R3 est éthyle, Met est Al, Fe, TiOq ou Zn, n vaut de 2 à 3 et q = (4 - n) / 2; un polyphosphate de mélamine ayant un degré de condensation moyen de 2 à 100 en tant que constituant F; un antioxydant phénolique à empêchement stérique en tant que constituant G et/ou un phosphite organique et/ou un phosphonite organique en tant que constituant H. Ces compositions de polyamide peuvent être employées pour la production de fibres, de films et de corps moulés, notamment pour des applications dans le domaine électrique et électronique.
PCT/EP2018/071443 2017-08-11 2018-08-08 Compositions de polyamide ignifuges et leur utilisation WO2019030250A1 (fr)

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